Electrochiroptical response of 2,2′-(2,2-diarylethenyl)binaphthyl-type electron donors that undergo reversible C-C bond formation/breaking upon two-electron transfer

2,2′-[2,2-Bis(4-dimethylaminophenyl)ethenyl]biphenyl (1) is a strong electron donor that undergoes oxidative C-C bond formation to give a stable dication rac-2 ²⁺ , the 9,10-dihydrophenanthrene derivative substituted with two bis(4-dimethylaminophenyl)methylium chromophores. This dication salt regenerates the starting diolefin 1 by reductive C-C bond breaking, thus realizing a new electrochromic system with high electrochemical bistability and a vivid change in color from yellow to deep blue. Similarly, the binaphthylic diolefin rac-3 and the helicene-type dication rac-4 ²⁺ are interconvertible upon two-electron transfer. Both the UV-vis and CD spectra changed drastically upon electrochemical transformation between optically pure 3 and 4 ²⁺ , which represents a new electrochiroptical system.